Exhaust process for the dyeing of synthetic fibre materials

ABSTRACT

Exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents wherein are used as dyestuffs sulphonamide group containing disperse dyestuffs. There are obtained without originating waste waters dyeings with excellent fastness to washing, rubbing, light and sublimation.

United States Patent [1 1 Neeff 1 1 June 24, 1975 1 EXHAUST PROCESS FOR THE DYEING OF SYNTHETIC FIBRE MATERIALS [75] Inventor:

I73] Assignee: Bayer Aktiengesellschaft,

Leverkusen-Bayerwerk, Germany Riitger Neeff, Leverkusen. Germany (63] Continuation of Scr. No. 161,282. July 9. 1971,

abandoned.

[30] Foreign Application Priority Data July 10. 1970 Germany 2034264 May 18. 1971 Germany 2124495 May 18. 1971 Germany 2124496 [52] U.S. Cl. 8/39; 8/41; 8/42; 8/170; 8/174 (51 I Int. Cl C09!) 5/62 [58] Field of Search 8/39, 41, 42, 170, 174

[56] References Cited UNITED STATES PATENTS 3.524.718 8/1970 Nador ct a1. 8/170 Seuret et a1 4. 8/172 Neeif ct al. 8/174 X FOREIGN PATENTS OR APPLICATIONS 1,581,325 9/1969 France 1,153.22] 5/1969 United Kingdom 832.343 H1970 Canada 1.952.535 4/1971 Germany 1.192.984 5/1970 United Kingdom Primary ExuminerBenjamin R. Padgett Assistant Examiner-P. A. Nelson Attorney, Agent, or FirmPlumley & Tyner [57] ABSTRACT Exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents wherein are used as dyestuffs sulphonamide group containing disperse dyestuffs. There are obtained without originating waste waters dyeings with excellent fastness to washing. rubbing, light and sublimation.

12 Claims, N0 Drawings I EXHAUST PROCESS FOR THE DYEING OF SYNTHETIC FIBRE MATERIALS This is a continuation of application Ser. No. l6l,282, filed July 9. l97l, now abandoned.

The invention relates to an exhaust process for the dyeing of synthetic fibre materials from organic waterimmiscible solvents; more particularly it concerns an exhaust process for the dyeing of synthetic fibre materials from organic water-immisicible solvents wherein are used as dyestuffs disperse dyestuffs containing sulphonamide groups.

Organic water-immisible solvents suitable for the process according to the invention are those the boiling point of which lies between 40 and l7()C, eg. aromatic hydrocarbons such as toluene. xylene; and halogenated hydrocarbons. especially aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, l ,l-dichloroethane, l,2- dichloroethane, l ,l ,2-trichloroethane, l .1,l ,2- tetrachloroethane, l,l,2,2-tetrachloroethane, pentachloroethane. l-chloropropane, 2-chloropropane, 1,2- dichloropropane, l,l .l-trichloropropane. lchlorobutane, Z-chlorobutane, l,4-dichlorobutane, l-chloro-2-methylpropane, 2-chloro-2methylpropane or dichlorohexane; as well as aliphatic fluorinated and fluoro-chlorinated hydrocarbons. such as perflouro-nhexane, l ,2 ,2-trifluoro-trichloroethane and trifluoro-pentachloropropane; aromatic chlorinated and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene, l,l ,ltrichloroethane and l,l,l-trichloropropane have proved particularly satisfactory. Mixtures of the said solvents can also be used.

The sulphonamide group-containing disperse dyestuffs to be used according to the invention may be based on any type of dyestuffs, provided these contain at least one sulphonamide group. The dyestuffs to be used according to the invention may belong, for example, to the series of metal-containing or metal-free monoor polyazo dyestuffs or (azo)methine dyestuffs; to the series of anthraquinone dyestuffs and of condensation products thereof containing more than three fused rings", other suitable dyestuffs are oxanio, nitrodiphenylamine. naphthalic acid. diand triphenylmethane dyestuffs; naphtholactam condensation dyestuffs, quinophthalone dyestuffs, and dyestuffs based on naphthoquinone and naphthoquinonimine; as well as other condensation dyestuffs. In addition to the sulphonamide groups required by definition, the dyestuffs may contain other conventional substituents, such as halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, nitre, sulphone, optionally substituted carboxamide groups, optionally substituted or acylated amino groups, alkylthio and arylthio, hydroxy, hydroxyalkyloxy, aminoalkyloxy, cyano, cyanoalkyl, and differently substituted alkyl. aryl, aralkyl radicals. and the like.

The dyestuffs contain one or more sulphonamide groups which are linked to the aromatic nuclei of the on dis-cs -s 2 basic ring system of the dyestuff itself or to aryl; aralkyl. or aliphatic groupings in external positions. The number of sulphonamide groups preferably amounts to I to 3.

The sulphonamide groups are characterized by the formula in which the radicals B and B,, independently of one another, denote hydrogen or optionally substituted lower alkyl or alkenyl groups, aryl radicals or heteroaryl radicals. Furthermoreo, the radicals B and B, together may form a ring which may be interrupted by hetero atoms.

Examples of radicals B and B are the methyl. ethyl or trifluoromethyl radicals; the B-hydroxy, B-chloro, B-bromo, B-methoxy, B-methylthio, B-methylsulphonyl or B-cyanoethyl groups; or an ethylene or B-chloroor B-bromoethylene radical. If B or B. stands for an aryl radical, this is preferably a phenyl radical which may be substituted by one or more halogen atoms such as fluorine, chlorine or bromine; nitro groups; trifluoromethyl, hydroxy or lower alkoxy radicals; carboxyl or carboxamide groups; acylamino groups; sulphonamide or lower alkylsulphonyl radicals. Suitable heteroaryl radicals are, for example, the pyridyl, pyrrolyl, pyrimidinyl, furanyl, thienyl or sulpholanyl radicals. Examples of rings which may be formed by B and B, and may be interrupted by hetero atoms are the pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl or thiomorpholinyl dioxide rings.

Dyestuffs containing sulphonamide groups are known in large numbers and are prepared by conventional methods in that suitable dyesyuff intermediate containing one or more sulphonamide groups linked to the nucleus or in an external position are converted into the desired final products while retaining the sulphonamide groups and, if desired, further conversion reactions are carried out in the latter. Obviously, it is also possible to start from dyestuffs containing one or more sulphonic acid groups and to convert the sulphonic acid groups into the corresponding amides in the usual way via reactive intermediate stages, such as e.g. the ester and the acid chloride. In the case of aze dyestuffs, the usual conversion reactions are diazotisatien and coupling; for most other dyestuffs classes they are condensation reactions.

Examples of suitable azo dyestuffs containing sulphonamide groups are the following compounds in which the radical may have the following meaning:

R1, R2, R3, R H, 033, 8 OCH:

R I It, O1-0 -llky1, 0 -0 4mm, lryloxy B I H, hll, 0 -0 -a1kyl, 0 -0 -l1koxy, -IB-Acy1 B B I a, 0x 0 x Un -03 .08, GE JE OH .mmn,

h I 31 R s s mu -u R I H, c -fl alkyl, c -fl nlkoxy, nryloxy R 8, I231, C -c alkyl, 0 G -a1kcxy, din-icy].

a a H, CH3, 0 x c11 .ca .oa, .CH .0B .0.acy1, .ca .cu .0I

I I JJ 0 5 H, CH5, D-QaK-y, $3 8 0K 0 11 860- G H 03 M 08, 011 33 00008 5 I O i H I In 15- A! a l a a I 011 c 11 c a l Sunable anthraqulnone dyestuffs are. for example. 2 {mg those in which one or more sulphonamide groups stand 1 3 in the anthraqunione molecule itself or in aryl or alkyl cw h0z-li\ l radicals which are linked to the anthraquinone molecule via bridge members such as amino, ether thioe a ther, sulphonamide 0r sulphonylamino groups.

The anthraquinone compounds may have the following constitutions, for example. the group 2 3 3 3 -so d! Q 2 \81 having the same meaning as above:

B l 430 H\ B -0 l 1 I ll 1 I t 0 m 0 m Cntinued ID mari -N 0 mil l B n 13- (CH2 n-SDz-ll 0 I I R I 0 E3 on. 1 I OH,

furthermore. ucylution products of aminounthruquinones, e.g. of the formulae:

I 5 O'n.lkyl (ax-71) ll 0 N82 so 0 on 2 m l I l n 3 0 H3 H 5 0 on 9 m (.1 on

I I 0 00x 0 on m r: m.cn .cn .on 2 m I HO O HH'OH 'GD' 'OH O m m n 0 an; 40

8 H 0 m 0 m H2" 0 m 0 mg with sulpho-carboxylic acids of the general formula /B riooc-x-so -n B X alkylene, arylene, a bivalent heterocyclic radical,

or with a compound of the formula and furthermore. the anthruquinone dyestuffs assembled in the following Table:

l7 18 The anthruqunione dyestuffs of the formula 0 KH I -s- -so m1-@ on 0 R ll II II I 0 R 0 EH in which 10 -o-/ so rm-G-oa R means an amino group U 2 R means a hydroxy or amino group n X means O or S Y means a phenylene group and D means 15 and Among anthraquinone condensaton products which contain sulphonamide groups and contain more than have proved to be of special interest and among them 20 thre fused rings, the following may be mentioned by the dyestuffs way of example: Isothiazoloanthrones, such as further-on, dyututtl at the type ,I I I x i-alkyl 802-I\'1 u-unm I20 I Anthraquinone dyestuffs of the formulae given above are prepared according to the synthesis principles known in anthraquinone chemistry. Condensation reactions with appropriate starting compounds are suitable in the first instance for this purpose. For example, amino group-containing anthraquinone compounds in which the amino groups stand either in an external position or, preferably, in a position linked to the nucleus, can be condensed with suitable sulphoaryl-acid halides or anhydrides, e.g. sulphophenylor naphthylcarboxylic acid or -sulphonic acid chlorides or bromides to form the corresponding acid amides; or, for example, anthraquinone compounds with mobile halogen atoms can be reacted with sulphoaryl-amines such as sulphophenyl-or sulphonaphthyl-amines to form the corresponding sulphoarylamino-anthraquinone derivatives. and the free sulpho groups still present in the resultant dyestuffs can be converted into sulphonamide groups in known manner. Alternatively, for example, anthraquinone compounds containing amino groups can be condensed with sulphonamido-aryl-acid halides or anhydrides, or e.g. anthraquinone compounds containing mobile halogen atoms can be condensed with sulphonamido-arylamines.

Anthraquinone ether and thioether derivatives in which sulphonamide groups are contained in alkyl, aralkyl or aryl radicals of the ether or thioether component. can be prepared according to similar synthesis principles. Another possibility of synthetising sulphonamide group-containing anthraquinone dyestuffs to be used according to the invention consists in that anthraquinone-acid halides, such as carboxylic acid and sulphonic acid chlorides or bromides, are converted into the corresponding amides or esters with the aid of suitable amino or hydroxy compounds which contain at least one additional sulphonamide group. Obviously, it is also possible to use for the present process also those anthraquinone compounds in which one or more sulphonamide groups stand in a position linked to the nucleus or in which sulphonamide groups linked to the nucleus as well as externally linked sulphonamide groups are present.

As representatives of nitro dyestuffs containing sulphonamide groups, there may be mentioned for example dyestuffs of the formula 2 R1 R3 mg 34 X SO or CO -NH or O- Z and/or Z,

R R H. Cl, Br, F, CH C H CH O, OH, CN,

2. R R CFB, COOH, OCH COOH, -OCH 5 -COOH, -COOalkyl, -NH-acyl.

,s ,n ,3 k 0 K -0-0H -Oa -cou cn orr, cu -ca es, -N!!-(0B -fl0 -H 1 or dyestuffs of the formula R i R DQ- -Q R in which R, means hydrogen a halogen atom, a trifluoro, cy

ano, hydroxy, C,C -alkyl or -alkoxy, a hydroexmethyl or -ethyl. a hydroxy-ethylene-oxy, acylamino. alkylsulphonyl-amino alkylsulphone, carboxamide. aminosulphonyl-alkyleneamino or sulphonamide group;

R means hydrogen or a (I -C alkoxy group;

R means hydrogen, a halogen atom. a hydroxy. hydroxy-ethyleneoxy carboxamide. aminosulphenylalkylensoxy or sulphonamide group;

X stands for the group SO or CO; and

Y stands for NH or O;

with the proviso that one of the radicals R,, R or is a sulphonamide group or a radical containing a sulphonamide group.

The nitro dystuff of the formula has proved to be especially valuable.

in many cases it has proved advantageous for the dyebaths to contain small amounts of water, i.e. up to l per cent by weight, preferably 0.5 per cent by weight, referred to the weight of the organic solvent.

Furthermore. it has proved expedient in some cases to add non-ionic auxiliaries to the dyebaths. Suitable nonionic auxiliaries are primarily the known interfaceactive ethoxylation and propoxylation products of fatty alcohols alkylphenols. fatty acid amides and fatty acids as well as mixtures thereof; the auxiliaries are used in an amount of 0.05 2 per cent by weight referred to the weight of the organic solvents. instead of being immediately added to the dyebaths. the auxiliaries can also be used to advantage for pasting the sulphonamide group-containing dyestuffs and in this way be added to the dyebaths in the form of a dyestuff/auxiliary paste.

The synthetic fibre materials to be dyed according to the invention are primarily fibre materials of polyesters, such as polyethylene terephthalate. polycyclohexanedimethylene terephthalate, heterogeneous polyesters from terephthalic acid, sulphoisphthalic acid and ethylene glycol or copolyester ester fibres from phydroxybenzoic acid, terephthalic acid and ethylene glycol; cellulose triacetate cellulose 2 /2-acetate; polyarcylonitrilc; synthetic polyamides such as hexamethylene-diamine adipate. poly-e-caprolactam or 4- aminoundecanic acid; and polyurethanes. The fibre materials may be present in the most varied stages of processing, for example. as threads loose material, combed material. yarn as piece goods such as fabrics or knitted fabrics, or as ready-made goods.

Dyeing according to the invention is preferably carried out in closed apparatus, for example, by introducing the fibre materials at room temperature into the dyebath, heating the dyebath to 60l70C and keeping it at this temperature until the bath is exhausted; this is usually the case after 60 minutes. After cooling to room temperature, the liquor is separated and the fibre materials are freed from any adhering solvent optionally after a short rinsing with fresh organic solvent, by filtering with suction or by centrifuging and subsequent drying in a warm current of air. With the aid of the process according to the invention it is possible to dye synthetic fibre materials from organic solvents in a simple way, high dyestuff yields and excellent fastness properties being achieved.

The sulphonamide group-containing dyestuffs to be used according to the invention are largely insoluble in the organic water-immiscible solvents. They are distinguished from the dyestuffs hitherto used for dyeing synthetic fibre materials from organic solvents by their substantially better affinity and an increased fastness to sublimation.

It may be mentioned that mixtures of the dyestuffs to be used according to the invention sometimes gives a better dyestuff yield than the individual dyestuffs. The parts given in the following Examples are parts by weight.

EXAMPLE I Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from 1 part of the monoazo dyestuff 4-aminobenzenesulphonic acid amide 3-methyl-pyrazolone-(5) and 1000 parts tetrachloroethylene.

The bath is heated to l 15C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current A strong yellow dyeing of excellent fastness to sublimation and very good fastness to washing and light is obtained.

An equally satisfactory yellow dyeing was obtained in the same way on a fabric of polycyclohexanedimethylene terephthalate fibres.

Yellow dyeings of equally satisfactory fastness properties were also obtained when the dyestuff mentioned above was replaced with the same amount of one of the following monoazo dyestuffs:

amide l-phenyl-S-pyrazolone-3-carboxylic acid amide Continued Example Dyestuff Shade 13 3-nitro-4-aminobenzene-sulphonic acid yellow amide l-phenylpyrazolone-3-carboxylic acid ethyl ester 14 2-methoxy-4-nitro-aniline l-(3-aminoyellow sulphonyl-phenyll-3 methyl5-pyrazolone l5 4-amino-benzene-sulphonic acid-(di-Z- yellow hydroxyethyll-amide l-(2cyanoethyl)3- methyl-S-pyrazolone lo 4-amino-benzene-sulphonic acid ethylamide yellow l(2-carboxyethyll-3-methyl-5-pyrazol0ne l7 2-cyano-4-nitro-aniline l-(3-aminoyellow sulphonyl-phenyl)-3-methyl5-pyrazolone 18 4 methyl-anilino l-(3-phenylaminoyellow sulphonyl-phenyll-3-methyl-5-pyrazolone l9 4-amino-benzene-sulphonic acid-dimethylyellow amide l(3-aminosulphonyl-phenyl)-3- methyl-5-pyrazolone 20 3-nitro-4-amino-benzene-sulphonic acid diyellow methylamide l(3chlorophenyl)5-pyrazolone- S-carboxylic acid 21 2-methoxy-5-nitro-aniline l-(2aminoyellow sulphenyl-ethyl)-3-methyl-5-pyrazolone 22 2-bromo-4-nitro-aniline l-hydroxy-benzeneyellow 2-sulphonic acid-(di-Z-cyanoethyl)-amide 23 4-ethoxy-aniline Lhydroxy-S-methylyellow benzene-Z-sulphonic acid-(4-chlorophenyll amide 24 4-(4-pyrrolidinesu|phonylbutoxy)-aniline yellow l-hydroxybenzene-Z-sulphonic acid (2- pyridino)-amide 25 3-amino-benzoic acid l-hydroxy-benzeneyellow 2-sulphonic acid-(3sulpholanyl)-amide 26 4-amino-benzene-sulphonic acid amide 1 yellow hydroxy4-methyl-benzene 27 Z-aminobenzene-sulphonic acid amide lyellow hydroxy-4-cyclohexyl-benzene 28 3-nitro4-aminobenzene-sulphonic acid amide yellow l-hydroxy-4 methyl-benzene 29 3nitro-S-chloro-4-amino-benzene-sulphonic yellow acid l-hydroxy-4-methylbenzene 3O 4-aminobenzene-sulphonic acid-piperidide yellow l-hydroxy-4-methyl-benzene2-carboxylic acid 31 4-amino-benzene-sulphonic acid-(Z-methylyellow sulphonylethyl)amide lhydroxy-4- methyl-benzene-Z-sulphonic acid amide 32 4-methylsulpenylaminoaniline l-hydroxyyellow 4-n-propyl-benzene 33 4-phenylsulphenylamino-aniline l-hydroxyyellow 4-methyl-benzene 34 4-dimethylamino-sulphonylamino-aniline I- yellow hydroxy-4-ethyl-benzene 35 4-methylsulphonylamine-aniline l-hydroxyyellow 4-methyl-benzene-2-carboxylic acid amido EXAMPLE 36 24 1 part of the monoazo dyestuff 4-piperidyllsulphonylamino-aniline l-hydroxy-4- methylbenzene.

1000 parts tetrachloroethylene 1.5 parts oleic acid ethanolamide 1.5 parts oeyl alcohol eicosaethylene glycol ether and 6 parts of water The bath is heated to 78C within 20 minutes and kept at the same temperature for minutes. After separation of the dye liquor and rinsing with fresh tetrachloroethylene, the dyed material is freed from the adhering solvent by filtering with suction and drying in an air current. A brilliant yellow dyeing is obtained.

EXAMPLE 38 100 Parts of yarn of polyacrylonitrile fibres are dyed in a dyebath prepared as described in Example 36. The bath is heated to 100C within 20 minutes and kept at the same temperature for 30 minutes. After the usual washing and drying, there is obtained a yellow dyeing of good fastness properties.

EXAMPLE 39 100 Parts of a fabric of polyethylene terephthalate fibres are heated in a dyebath containing 1 part of the monoazo dyestuff 3-nitro-4-aminobenzene-sulphonic acid amide l-methyl2,4- dihydroxy-quinoline in 1000 parts tetrachloroethylene 100 Parts of a fabric of triacetate fibres are introduced at room temperature into a dyebath prepared from dyestuff 4-methyll-hydroxy-4-methyl- 1 part of the monoazo sulphonylamino-aniline benzene and 1000 parts tetrachloroethylene.

EXAMPLE 37 100 Parts of yarn of acetate threads are introduced at about 22C into a dyebath prepared from 5 Example Dyestull Shade 40 4-amino-benzene-sulphonic acid amide yellow l-methyl-2.4-dihydroxy-quinoline 4i 4-trifiuommethyl-2-arnino-henzeneyellow sulphnnlc acid amide -v l-methyl-ZA- dih droxy-quinoline 42 4-chloro'3-amino-benzenesulphonic acid yellow (2-hydroxyethyl)amide l-methyl-2 4- dihydroxy-quinoline 43 4-aminobenzene-sulphonic acid-(di-Z- yellow hydroxyethyll-amide l-methyl'2.4 dihydroxy-quinoline 44 3-amino-henzene-sulphonic acid-t Z-methylyellow thioethyU-amide l-methyl-2.4- dihydroxy-quinoline 45 4-amino-benzene-sulphonic acid-( l-naphthyllyellow amide l-methyl-2,4-dihydroxy-quinoline 46 i 3,5-dichloro-4-amino-henzene-sulphonic acid yellow dimethyl-amide N-[2-cyanoethyl)-N- ethyl-aniline 47 3.6-dichloni-4-amino-henzene-sulphonic acid orange dimethyl-amide N [2-cyanoethyl)-N- eth l-aniline 48 3-mlro-4-amintrhenzenesulphonic acid amide reddish N,N-(di-2-acetoxyethyl )-aniline yellow 49 3-nitro-5-bromo4-amino-benzene-sulphonic yellowish acid amide N,N-ldi-2-acetoxyethyl)- red aniline V I 50 3-nitro-4-amino-benzene-sulphonic acid reddish amide 3-methyl-N,N-ldi-Z-acetoxyyellow ethyl l-aniline 5 l 3-cyano-5-nitro-4-amino-henzene-sulphonlc yellowish acid methylamine N'ethyl'N-(2-acetoxyred ethyl)-aniline g 52 3,5-dicyano-4-amino-bemene-sulphomc acid red amide H N.N-dimethyl-aniline ominued Shade 3-chloro-5-nitm-Z-amino-benzene-sulphonic acid amide N.N-(di-Z-propionyloxyethyl l-aniline 3-chloro-5-nitro-Z-amino-benzene-sulphonic acid N.N-(di-2-methoxycarbonyl ethyl l-aniline 3-cyano-5-nitro-2-amino-benzene-sulphonic acid amide 3-methyl-N.N-(di-2- methoxycarbonyloxy-ethyl l-aniline 3.5-dichliiro-4-amino-henzene-sulphonic acid methylamide N-(Z-pyrrolidylcarhonylethyl l-aniline 3-cyano'5-hromo-4-amino-benzene-sulphonic acid diethylamide N-l2-(3-methylphenylamino )-ethy| I-succinimide -methoxy-2-aminobenzene-sulphonic acid amide N-( 2-cyanoethyl)-N-( Z-hydroxyethyl l-aniline 3-hromo-S-nitro-4-amino-benzene-sulphonic acid amide 3-acetylamino-N.N-dimethyl aniline 3-hromo-5-cyano-4-amino-benzene-sulphonic acid amide J-acetyIamino-N N-diethyl aniline 3,5-dicyano4-amino-benzene-sulphonic acid amide 3-acetylamino-N.N-dimelhylanilinr 3-bromo-5-nitro4-amino-hemene-sulphonic acid amide 2-methoxy-S-acetylamino- N N-dimethyl-aniline 3-chloro-5-nitro-Z-amino-benzene-sulphonic acid amide Z-phenoxy-S-acetylamino N,N-dimcthyl aniline 2-hromo-4.fi-dinitroaniline 3-mcthylsulphonylamino-N.N-dimethylaniline 2-hromo-4-nitro-fv-cyano-aniline 3-chloromethylsulphonylamino N Z-cyanoethyl l-aniline 2 6-dicyano 4-nitro-aniline 3-methylsulphonylamino-N.N-dimethylaniline 2-hromo-4 6-dinitro-aniline 3-phenylsulphonylamino-N,N-dimethyl-aniline 2-chloro-4.6'dinitro-aniline 3-methylsulphonylamino-N-I Z-hydroxyethyl ]-N( Z-cyanoethylJ-aniline 2-hromo-4.fi-dinitro-aniline Z-methoxy- 5-methylsulphonylamino-N.N-ldi-Z- acetoxyethyh-aniline 2.6-dichloro-aniline 3-dimelhylsuIphonyl-amino-N.N-(di-Z-acetoxyethyll-aniline 3-hromo-5-nitro-4-amino-henzenesulphonic acid amide 3-methylaminosulphonylmethylamino-N.N-dimethylaniline 2-chloro-4-nitro-6-cyano-aniline 3-l 3-ethylaminosulphonylpmpylamino)- N.N-diethyl-aniline 2,6-dichloro-4-nitro-aniline N-ethyl-N-( Z-dimethylaminosulphony] ethyl l-aniline 4-dimethylsulphonylarnino-aniline 3-methyl-N.N-(di-Z-acctoxyethyl)- aniline 3-nitro5-amino-hen2enesulphonic acid (Z-hydroxyethyl l-amide N-( Z-methoxyeth l ]-N-( Z-rnethoxycarbtmylethyl aniline 2-hromo-4.fi-dinitro-aniline N-melhylsulphonyl-aniline 2.5-dichloro-anilinc 3-methyl-N- ethyl-N4 Z-methylsuIphonylaminoethyl l-aniline 4-amino-benzene-sulphonic acid methylamide N-phenylaniline 4-amino-henzene-sulphonic acid-thinmorpholid-S-dioxide 4-( 3-methylaminosulphonyl-benzoylaminol-aniline 4-methyl-phenol o-methylaminosulphon I-Z-aminol .3- benzothiazole N-l ..-cyanoethyl)-N- (I-acetoxyethyl l-aniline 6-aminosulphonyl-Z-aminol .J-benzuthiazole N.N-(di-2-cyanoethyl)- aniline 3chloro-4-aminwhenzenc-sulphonic acid amide D J-acetylamino-N.N-diethylaniline 5methylaminosuIphonyl-2-amino- LS-thiarple N-ethyl-N-( Z'carboxyethyl )-aniline 5-aminosuIphonyI'Z-arnino- I .3-

thiazole 3-acetylamino-N.N-dimelhylaniline 4-( 4-amin0sulphonylphenyl )-2-amino- 1,3.5-thiadiazole N.N-di-2-acetoxyethyl l-aniline yellowish red violet redviolet violet violet violet violet blueviolet blue violet violet blue reddish yellow brown brown yellowbrown reddish yellow orange yellow reddish yellow yellow yellow yellow red red

orange bl u is h red red' violet yellowish red lmmplc l) \c-tul l -(onl1uucd Shade R7 4-[ 4-methylaminosulphonylphcnyl )-2 amino-l.3.5-thiadia7ole J-acetylml aminoN.Ndimethyl-aniline 88 4 methylsul honvlamino-aniline S-methyl-N. -(di-2-acetoxyethyl)- "range aniline 89 4 phenylsulphony-lamino-Z-chloro-aniline 3-acetylamino'aniline 90 2-chloro-4-nilro-aniline 2-amino- "range naphthalene-o-sulphonic acid methyl-amide red 9| 2-chloro-4-nitro aniline Z-amini naphthalene fi-sul honic acid amide rad 92 4-methylsulphony amino-Z-nitro-aniline Z-hydroxynaphthalene red 93 4-methylsulphonylaminoaniline 2-aminonaphthalene-S-sulphonic acid red methylamide 94 4-amino-benzene-sulphonic acid amide I ,l-dimethyI-indole 95 4-aminoazobenzene Z-hydroxynaphthalene ti-sulphonic acid-N-methylred N-( Z-hydroxyethyl )amide 96 4-aminoazobenzene Z-hydroxynaphthalene-6sulph0nic acid Nmethylred N-( Z-acetoxyethyl )amide 97 4-amino-azohenzcne4'-sulphonic acid amide Z-hydroxynaphlhalene red 98 3-chloro-Sarnino-benzene-sulphonic acid amide N,N-(di-acetoxyethyl)-aniline reddmh 99 4-methyl-5aminosulphonyl-2-amino- I ,3- yellow thiamle B-acetylamino-N,N-dimethylred aniline I00 5-nitro-3-amino-benzoisothiazole4 2 l 3-rnethylsulphonylaminoN,N-dimelhylaniline l0] 5-nitro3-amino-benzoisothiazole-I2.I red fi-sulphonic acid amide B-acetylamino- N,N-dimelhyl-aniline EXAMPLE I02 100 Parts of a knitted fabric of polyethylene terephthalate fibres are dyed in a dyebath containing l part of the disazo dyestuff 4-amin0benzene-sulphonic acid amide aniline phenol in 1000 parts tetrachlorethylene at C for 30 minutes. After the usual rinsing and drying, there is obtained a reddish yellow dyeing of very good fastness to sublimation, washing and light.

Dyeings of equally valuable fastness properties were also obtained when the above dyestuff was replaced with the same amount of one of the fol dyestuffs:

lowing disazo Example Dyestul'f Shade I03 4-amino-henzene-sulphonic acid methylreddish amide 2.5-dimethoxy-aniline phenol orange I04 3-chloro4-amino-henzene-sulphonic acid orange I4-chlorophenyU-amide 2-chloroaniline phenol I05 S-amino-toluene 3-ethoxy-aniline orange I-h 'dmxy-benzene-2-sulphonic acid-I 2- hy roxyethyll-amide I06 4-cl1loro-3-amino-henzene-sulphonic acid reddish arnlde 3-amino-toluene salicylic yellow act I07 3-nilro-4-amino-benzene-sulphonic acid reddish amide B-amino-ethylbenzene phenol yellow I08 2-amino-benzene-sulphonic acid amide reddish aniline salicylic acid amide yellow I09 4-amino4oluene Lamino-benzeneyellow sulphonic acid amide phenol ll0 2,5-dichloro-anilinc aniline 3- orangehydroxy-N-(4-aminosulphon lbutyh-aniline brown I l l 4-methylsulphonylamino-ani ine 3-aminoreddish toluene phenol yellow I I2 44 3-methylaminnsulphonylpropylaminolreddish aniline 3-methoxy-aniline phenol yellow I I3 4-( 4-methoxyphenylsulphonylaminolaniline 3-amino-ethylbenzene phenol Radish I I4 4-amino-henzene-sulphonic acid amide yellow l-aminonaphthalene phenol orangfi sulphonic acid amide phenol EXAMPLE 122 50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from 1 part 1-amino-4-hydroxy-2-(4'aminosulphonylphenyl thio-anthraquinone 1.5 parts oleic acid ethanolamide 1.5 parts oleyl alcohol eicosaethylene glycol ether 6 parts of water and 500 parts tetrachloroethylene.

The bath is heated to 120C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor. the dyed material is rinsed with fresh solvent at 40C and. after removal of the rinsing liquor, dried in an air current. A brilliant violet dyeing of excellent fastness to light and sublimation is obtained.

Equally satisfactory violet dyeings are obtained when the 500 parts tetrachlorethylene are replaced with the same amount of 1,1,2-trichloroethane, l,1,l,2 tetrachloroethane, 1,1,2.2,-tetrachlorethane, pentachloroethane, 1,2-dichloropropane, 2-chlorobutane,

1,4-dichlorobuutane, perfluoro-n-benzane, 1,2,2-trifluoro-trichlorethane, trifluoro-pentachloropropane, chlorobenzene, fluorobenzene, chlorotoluene or benzotrifluoride.

The dyestuff used in Example 122 had been prepared as follows: parts l-amino-4 hydroxy-2-phenylthioanthraquinone are dissolved in 76 parts chlorosulphonic acid, and 22.5 parts thionyl chloride are added at -25C within 1 hour. The melt is stirred at 2025c for 3 hours, turned out on to ice, the precipitate is filtered off with suction and washed with icewater until neutral. The product is subsequently introduced into 250 parts of ammonia and stirred at 2025C for 5 hours. It is filtered off with suction, washed with water, and after drying there are obtained 18.5 parts l-amino-4-hydroxy-2-(4- aminosulphonylphenylthio)-anthraquinone 96 percent of theory.

EXAMPLE 123 100 Parts of fibre yarn of poly-E-caprolactam are introduced at room temperature into a dyebath containing 1 part of the dyestuff mentioned in Example 122 in 1000 parts tetrachlorethylene.

The bath is heated to 100C within 20 minutes and kept at the same temperature for 40 minutes while the liquor is vividly circulating. After this period of time, the Iiquor is separted. the dyeing is briefly rinsed with fresh solvent and dried in an air current after centrifuging. A brilliant violet dyeing of good fastncss properties is obtained.

An equally satisfactory dyeing was also obtained on yarns of polyhexamethylene-diamine adipate fibres.

The strength of colour of the dyeing can be increased by 10 percent by the addition of 1 part oleic acid ethanolamidc 1 part oleyl alcohol eiscosaethylene glycol ether and 4 parts of water to the dye bath.

EXAMPLE 124 Parts polyethylene terephthalate fabric are dyed at C for 30 minutes in a dycbath consisting of 1 part 1-amino-4-hydroxy-2-(4-methylaminosulphonylphenoxy)-anthraquinone.

3 parts oleic acid ethanoloamide 3 parts oleyl alcohol eicosaethylene glycol ether 12 parts of water and 160 parts tetrachlorethylene.

After rinsing with fresh tetrachlorcethylene and drying, there is obtained a strong and brilliant red dyeing of very good fastness to sublimation. washing and light.

When the above dyestuff was replaced with the same amount of one of the dyestuff listed in the following Table, then dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

Example Dyestuff Shad l-aminn-4-hydroxy-2-[4-t Z-methoxyethylred amino )-sulphonyl phenoxy l-anthraquinone 12o l-amino-4-hydroxy2-l 4l 2hydroxyethylred am ino )-sulphunyl-phenoxy ]anthraquinone l 27 l-amino-4-hydroxy-6-chloro 2-(4-aminored sulphonyl-phenoxyyanthraquinone 128 lamino-4-hydroxy-(aJ-difluoro-Z- red t4-thiomorpholino-sulphonyl-phenoxy anthraquinone E2) lamino-4-l1ydroxy-2-(4-methylsulphonylred aminnphenoxy l anthraquinone 130 1 amino-4-hydroxy-2-l 2-( 4-aminosulphunylred phenoxy)-ethoxy l-anthraquinone I31 l-amino4-hydroxy-Z-| 2-(4-methylaminw red sulphonylphenyl l-ethoxy l-anthraquinone 132 1-amino 4-hydroxy-2-l4-aminosulphony| red phenylthiol-ethoxy lanthraquinone 133 1-amino4-hydroxy2-t4-diethylaminored sulphonylamino-phenoxyl-anthraquinone 134 1-amino-4-hydr0xy-2-[4-t3-methoxyviolet propylaminol-sulphonylphenyl-thiolanthraquinone 135 l-aminn-4-hydroxy-2-l 4-( Z-hydroxyviolet ethylaminul-sulphonyl-phenyl-thio l anthraquinone 13h jumino-4-hydroxy -2-| 4-chloro-2-l Lli-2- violet hydroxyethyl )-amino-sulphonyl-phenylthin l-anthraquinone 137 jamino-4-hydroxy-2-tmmethylthio-Iiviolet amino-sulphonyl-phenyl-thio)-antl1raqumone 138 l-amino4-hydroxyJ-chloro-Z-l Z-methylviolet sulphon lethyl I-amino-sulphonyLphenyL thio |-anthraquinone l3! l-amino-4-hydroxy-2-t S-aminosulphonylbluish propylthiu)anthraquinune red I41) l-amino 4-hydroxy-2-(4-methylaminobluish sulphonyl-henvylthio l-anthraquinone red I41 l-amino-4-hytlrnxy-Z-l 2-(4-hexamethylenebluish imino-sulphonyl-phenyl j-ethylthio red anthruquinone I42 l-amino-4-hydroxy-2-l 2-( 3'methyl-4- bluish aminusulphonyl-phenoxy l-ethyl thio red anthraquinone Fmrnple Dycstuff J nnlmilcd Shade I 43 I -amino-4-hydroxy -Z-1 Z-dimcth lamim bluish sulphonylethylthio l-anthruquinone red I 44 I -;imino-4-methoxy-2-l 4-methylaminoyellowsulphunyl-phcnosy )anthraquinone red I 45 I -amino-4-mcthoxy-Z-l J-N-methyl-N- red s phenylamino-sulphonyl-phen)llhioI unlhraquinone I46 I -arnino2-I -1-morpholinosulphonylorange phenoxy I-anlhraquinune I47 I-amino-2-l4-aminosulphonyI-phenyl-thio)- yellowanthraquinone red I48 I -4'dihydroxy-2-|4-Il-cyanoethylaminmorange sulphonybphenuxy I-anthraquinone I49 I ,4-dihydroxy-2-( 4-aminosuIphonyl-phenoxy)- orange anthraquinone I SII I .4-dihydroxy-2-t 4-melhylaminoscarlet suIphonyl-phenyI-thio)-anthraquinone I I I .4-diamino'2 [4-( icyano-pheny l-amino bluesuIphonyI-phenoxy I-anthraquinone violet I 52 I .4-diamino-Z,3-bis-I4-amino-sulphonylredphenoxy I-anthraquinone violet I53 l.-8-diamino-2-( 4-amino-suIphonyl-phenylreddish thiol-anthraquinone blue I 54 I .4 diamino-2-[4-( 3-methoxypropylamino)- reddish sulphonvl-phenvl-sulphonyl l-anthraquinone blue I55 l.4-diamino'anthraquinone-l-sulphonic reddish 2 acid (4-ethyI-amino-sulphonyI-phenylIester blue I 56 I hydroxy-4-( B-methyIamino-sulphonyl bluephenyl amino) anthraquinone violet I57 l-hydroxy-4-( 4-methyl-3-aminu-sulphonyl bluephemlamino I-anthraquinone violet I 58 Ihydroxy4-l 4-methylsulphonyI-amino reddish phenyl-amino)z1nthraquinnne blue I 59 I -amino-4-[4-I Z-cyanoethyl-2hydroxy blur:

cthyl-amino-sulphonyl)-phenyl-aminoL ant raquinonc I 60 I -amino-4-( 2.6-diethyl-4-methyl-3 reddish amino-sulphonyl-phenyl-nmino)-;mthra blue quinone I6I I -amino-2-hromo-4-(4methoxy3-aminoreddish sulphonyl-phenyluminoI-anthraquinone blue I62 l-amino-2-phenyl-thio-4-l4-methyI-3- hlue amino-sulphonyl-phenylamino)-anthraquinone I 63 l-amino-2-phenyl-sulphonyl-4-( .i-aminogreenish sulphonyl-phenylumino)-anthraquinone blue I 64 I amino-44 4-nmino-sulphonylphenyl red thio)-anthraquinone I65 I -amino 2-l 4-am ino-sulphonyl-phenoxy pink 4-(4meth \'lphenylhsulphonyl-aminob anthraquinone I66 I -amino-2-t 4-amino-sulphonyl phenoxy I pink 4-methyI-sulphonyI-amino-anlhraquinone I67 I-amino-anthraquinone-Z-sulphonic acid red (4-methoxyphenyl-amidel I 68 I -amino-4-hydroxy-anthraquinone-Z- red sulphonic acid-I 3-trifluoromethyl-phenyl amide] I69 I.4-diamino-anthraquinone-Z-sulphonic acid blue amide I7ll l -'1'diuminu-anthraquinone-Z-sulphonic acid blue I 2-methoxy-ethyIJ-amide I71 I ,5-dihydroxy-4 ll-diaminwanthraquinone blue Z-sulphonic acid ethylamide I72 I .5-dihydnixy-4 8-diamino-anthraquinoneblue l6-disulphonic acid-l 3-methoxypropyl amide I 7. 1.4-diamino-2-l S-melhylaminosulphonylblue benmxamlyH 2 I I-anthraquinone I74 I amino-4-( 4-methylphenyLamino1- blue anthraquinone-Z-sulphonic acid-t Z-hydroxyethyl l-amide I 75 l-amino-4-cyclohexyl-amino-anthraquinoneblue Z-sulphonic acid amide I76 l-I 3-aminosulphonyl-propyI-amino)- red anthraquinone I 77' I ,4-his-( 3 amino-sulphonyl-propylhlue aminoJ-anthraquinone I 78 l,5 dihydroxy-4.il-diamino-Z-l 4-hydroxyblue 3-ethylamino-sulphonyI-phenyl lanthraquinone I79 I.S-dihydroxy-4.l-I-diamino-3-t 4 hydroxy blue 3-methylamino-sulphonyl-phenyl)-anthraquinone 6U lltll I .S-dihydroxy-li-nitm-4-( .l-ethylamint blue sulphonyl-phenvlaminoI-anlhraquinone I It I I ,ll-dihydroxy-s nitro-lt laminohlue suIphonyI-phenylamino l-anlhraquinone I 82 I rfi-dihydroxy -8-amino-4-t 3-methylaminoblue sulphonyl-phcnylaminoJ-anthraquinone I 83 l.8-dihydroxy-5-aminn-44 3aminoblue suIphonyI-phen)laminol-anthraquinone I84 l.5-dihydroxy-8-amino-xchlom-4- blue I3-amino-suIphonyI-phenylamino)- anthraquinone l-uimplc Dyestull unlmut-tl Shade I85 lj-dihydroxy -I'4-nitro-x-hromo4 blue I 3 amino-sulphonyl'phenylamino)- unthraquinone 1H6 l,Il-dihydroxy-5-amino-x-bromo-4- blue (3-;imino-suIphonyl-phenylamino I- anthraquinone I87 I .ll-dihydroxy-5-amino x hromo-4- blue (3-amino'sulphonyl-phenylamino)- anthruquinone I88 I .8-dihydroxy-5-methylamino-4- hlue I4-methyl-3-amino-sulphonyl-phenylaminoJ-anthraquinone I89 I.I-isnthiazolanthrone-Z-sulphonic acid yellow (4-bromo'phenyl I-amide I90 5[ laminosul honyl-ethylamino)- I ,9- yellow isothiazoloanlhrone l9] I,9-pyrazoloanthrone-Z-suIphonic acid-N yellow llhydroxyethyl l-N-phenyI-amide I92 5-( Z-amino-sulphonyl-ethylaminol- I 9- yellow pyrazoloanthrone I93 4 3-amino-sulphonyl-phenylamino red N-methyl- I .9-anthrapyridone I94 7-( Z-hydroxyethyl I-amino-sulphonylred 3.4'phthaIoyl-acrid0ne I95 7-( 3methoxyprnpyl )-aniino-sulphonyl- 2-amino-3,4-phthaloyI-acridone I96 I .8-naphthoylene-benzimidazole-Bz-3- yellow sulphonic acid methylamide I97 l.lI-naphthoylene henzimidazole4- yellow sulphonic acid amide I98 I ,8naphthoylene-benzimidazole-IS- yellow dicarboxylic acid-( Z-methoxy-ethylimide)- Bz-Il-sulphonic acid ethylamide I99 phthaIoylene-I l,8-naphthopyrimidine I yellow 3- or b-sulphonic acid amide 200 4( 3-amino-sulphonyl-phenyl amino yellow I 9-isothiaznlo-anthrone 2(Il 5 3amino-sulphonyl phenylamino yellow I ,9-isothiazoIo-anthrone 202 4-[ 3-methylumino-suIphonyLphenyI- yellow amino I-l .9-pyrazoIo-anthrone 203 SI 3-{ 2methoxyethyl-amino-sulphonyl yellow phenylamino I ,9-pyrazoIo-anthrone EXAMPLE 204 100 Parts polethylene terephthalate filaments are dyed in a dyebath consisting of I part 4-phenylamino-3-nitrobenzene-sulphonic acid amide 3 parts oleic acid ethanolamide 3 parts oleyl alcohol eiscosaethylene glycol ether 12 parts of water and 1600 parts of tetrachloroethylene at I I5C for 30 minutes while the liquor is vividly circulating, they are centrifuged and rinsed with tetrachlorethylene at 40C for 5 minutes. A strong greenish yellow dyeing of very good fastness to sublimination. washing and light is obtained.

An equally satisfactory dyeing is obtained when the tetrachlorethylene is replaced with the same amount of I ,l ,2-trichlorethane.

When I part 4-phenyIamino-3-nitrobenzenesulphonamide is replaced with a misture of 0.5 parts 4- phenyIamino-3-nitrobenzene-sulphonic acid amide and 0.5 parts 4-(4-methoxyphenyIamino-3-nitrobenzenesulphonamide, then a somewhat more reddish strong dyeing is obtained.

Similar dyeings are also obtained when the polyethylene terephthalate filaments are replaced with fibers of anion-modified polyethylene terephthalate (Dacron 64) or anion-modified polyhexamethylene-diamine adipate (Nylon T 844).

The dyestuff used in Example 204 had been prepared as follows: 900 parts of n-butanol saturated with ammonia are mixed with 550 parts of 79% 4-chloro-3- nitrobenzene sulphochloride and the mixture is stirred EXAMPLE 260 100 Parts of yarn of polyethylene terephthalate fibres are dyed in a dyebath consisting of or with a styryl dyestuff of the formula I s Olig-El-figS-Q-UGO-CiTg-Gll -F 45 -01! 1 part of the quinophthalone dyestuff of the formula i 2.5 parts oleic acid ethanolamide 2.5 parts oleyl alcohol parts of water and 1600 parts tetrachloroethylene as described in Example 204. A clear yellow dyeing is obtained, which is characterised by good fastness to sublimation, washing and light.

An equally satisfactory dyeing is obtained when the above quinophthaline-sulphonamide dyestuff is replaced with a bromination product which contains about l bromine atom per molecule and can be obtained in known manner by bromination in nitrobenzene or glacial acetic acid.

Clear yellow dyeings are also obtained when the dyestuff mentioned in Example 260 is replaced with equal amounts of the quinophthalone-sulphonic acid amides listed in the following Table:

R1 on c n it c EED s {B Greenish yellow dyeings are obtained when the quinophthalone-sulphonamide dyestuff mentioned in Example 260 is replaced with equal parts of one of the methine dyestuffs of the formulae 1 f a-cm-cooc ar, ca

cit

EXAMPLE 275 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning. into a dyebath prepared from 1 part l-amino-4-hydroxy-2-[4-(4-hydroxyanilinosulphonyl)-phenoxy]-anthraquinone and I000 parts tetrachloroethylene.

The bath is heated to l 15C within l0 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then seperated and the dyed material is rinsed with fresh solvent at about 40C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current.

There is obtained a strong red dyeing of excellent fastness to washing. light, rubbing and sublimation.

An equivalent red dyeing was obtained in the same way on a knitted fabric of poly-ecaprolactame.

EXAMPLE 276 50 Parts ofa fabric of polyester fibres are introduced at room temperature into a dyebath prepared from 1 part l-amino-4-hydroxy-2-[4-(4'- hydroxyanilinosulphonyl)-phenoxy]-anthraquinone and 1.5 parts oleic acid ethanolamide l.5 parts oleyl alcohol eicosaethylene glycol ether 6 parts of water and 500 parts tetrachloroethylene.

The bath is heated to C within l0 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After seperation of the dye liquor. the dyed material is rinsed with fresh solvent at 40C and, after removal of the rinsing liquor. dried in an air current. A brilliant red dyeing of excellent fastness to washing, rubbing, light and sublimation is obtained.

EXAMPLE 277 I00 parts of fibre yarn of poly-c-caprolactame are introduced at room temperature into a dyebath containmg l part l,4-diamino-2-[4-(4'-hydroxyanilinosulphonyl)-phenylthio]-anthraquinone in l000 parts tetrachloroethylene.

The bath is heated to 100C within 20 minutes and kept at the same temperature for 40 minutes while the liquor is vividly circulating. After this period of time. the liquor is separated. the dyeing is briefly rinsed with fesh solvent and dried in an air current after centrifuging. A brillant reddish blue dyeing of excellent fastness to washing, light, rubbing and sublimation is obtained.

An equivalent dyeing was obtained in the same manner on a yarn of poly-hexmethylene diamine adipate fibres.

EXAMPLE 278 100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperture. without previous cleaning, into a dyebath prepared from 1 part 4-(4-hydroxyphenylamino)-3-nitro-benzenesulphonic acid-4-(hydroxyphenyl)-amide and I000 parts tetrachloroethylene.

The bath is heated to l 15C within minutes and kept at the same temperature for 30 minutes. while the liquor is vividly circulating. The liquid is then separated and the dyed material is rinsed with fresh solvent at about 40C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current. A strong yellow dyeing of excellent fastness to washing, rubbing. light and sublimation is obtained.

An equivalent yellow dyeing was obtained in the same manner on a fabric of poly-e-caprolactame fibres.

EXAMPLE 279 50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from 1 part 4-(4-hydroxyphenylamino)-3-benzenesulphonic acid-(4-hydroxyphenyl )-amide 1.5 parts oleic acid ethanolamide l.5 parts oleyl alcohol eicosaethylene glycol ether 6 parts of water and 500 parts tetrachloroethylene.

The bath is heated to l C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40C for 5 minutes. After separating of the rinsing liquor, the dyed material is the dyed material is rinsed with fresh solvent at 40C and, after removal of the rinsing liquor, dried in an air current. A brillant yellow dyeing of excellent fastness to wasing. rubbing,

light and sublimation is obtained.

I claim:

1. Process for dyeing synthetic fiber material by exhaustion comprising introducing synthetic fiber material into a dyebath which is a dispersion consisting essentially of A. organic solvent B. anthraquinone dyestuff containing 1 to 3 sulfonamide groups and largely insoluble in said dyebath; and

C. up to W! by weight of said organic solvent of water; said organic solvent consisting of water immiscible aliphatic halogented hydrocarbon; and dyeing at a temperature of 60 to C for lU-bU min utes until the dyebath is exhausted; said anthraquinone dyestuff free of reactive groups,

acid groups and carboxamide groups having the formula in which R, is hydroxy or amino;

R is hydroxy, amino, phenylsulfonylamino or C C,-

alkylsulfonylamino;

R is hydrogen, chlorine or fluorine;

Y is a phenylene, ethylene-oxyphenylene, ethylenethiophenylene, C,-C -alkylene-phenylene or C -C, alkylerie; and

D is a sulfonamide group.

4. The process of claim I in which said anthraquinone dyestuff has the formula in which R, is amino; R is hydroxy or amino X is O- or S; Y is phenylene; and

D is

3,891,388 37 38 5. The process of claim 1 in which said unthraqui- 6. The process of claim 1 in which said anthraquinone dycstuff has the formula none dyestuff has the formula 0 N r- -Q 1;"12. -3 l \J LY NH,

'; 0 OH u n WV m 7. The process of claim 1 in which said sulfonamide :1 group has the formula B SO N and -N is /CH5 -NH2, -NH-CH -H CH :-ca; -m'c u NH-CH -GH -OH,

coax-0R 

1. PROCESS FOR DYEING SYNTHETIC FIBER MATERIAL BY EXHAUSTION COMPRISING INTRODUCING SYNTHETIC FIBER MATERIAL INTO A DYEBATH WHICH IS A DISPERSION CONSISTING ESSENTIALLY OF A. ORGANIC SOLVENT B. ANTHRAQUINONE DYESTUFF CONTAINING 1 TO 3 SULFONAMIDE GROUPS AND LARGELY INSOLUBLE IN SAID DYEBATH; AND C. UP TO 1% BY WEIGHT OF SAID ORGANIC SOLVENT OF WATER; SAID ORGANIC SOLVENT CONSISTING OF WATER IMMISCIBLE ALIPHATIC HALOGENATED HYDROCARBON; DYEING AT A TEMPERATURE OF 60* TO 170*C FOR 10-60 MINUTES UNTIL THE DYEBATH IS EXHAUSTED; SAID ANTHRAQUINONE DYESTUFF FREE OF REACTIVE GROUPS, ACID GROUPS AND CARBOXAMIDE GROUPS HAVING THE FORMULA
 2. The process of claim 1 in which Y is C1-C4-alkylene.
 3. The process of claim 1 in which said anthraquinone dyestuff has the formula
 4. The process of claim 1 in which said anthraquinone dyestuff has the formula
 5. The process of claim 1 in which said anthraquinone dyestuff has the formula
 6. The process of claim 1 in which said anthraquinone dyestuff has the formula
 7. The process of claim 1 in which said sulfonamide group has the formula
 8. The process of claim 1 in which said water-immiscible aliphatic halogenated hydrocarbon has a boiling point between 40* and 170*C.
 9. The process of claim 1 in which said synthetic fiber material is polyester, polyamide, cellulose, triacetate, cellulose 2 1/2 acetate, polyacrylonitrile, or polyurethane.
 10. The process of claim 1 in which said synthetic fiber material is polyester.
 11. The process of claim 1 in which said synthetic fiber material is polyamide.
 12. The process of claim 1 in which said dyebath contains 0.05 to 2 percent by weight of non-ionic dyeing auxiliary based on the weight of said aliphatic halogenated hydrocarbon. 